福岡工業大学学術機関リポジトリ

(1)

福岡工業大学学術機関リポジトリ

Synthesis of Liquid Crystalline

Nanosheet/Polyurethane Composite Elastomer Films

言語: jpn 出版者:

公開日: 2021-12-10 キーワード (Ja):

キーワード (En):

作成者: 宮元, 展義, 諸岡, 時希, 大背戸, 豊メールアドレス:

所属:

メタデータ

http://hdl.handle.net/11478/00001696

URL

(2)

⚟ᒸᕤᴗ኱Ꮫ◊✲ᡤᡤሗ㸦

2021

㸧

ᾮᬗᛶ↓ᶵࢼࣀࢩ࣮ࢺ / ࣏ࣜ࢘ࣞࢱࣥ」ྜ࢚ࣛࢫࢺ࣐࣮⭷ࡢྜᡂ

ᐑඖ ᒎ⩏㸦ᕤᏛ㒊⏕࿨⎔ቃ໬Ꮫ⛉㸧

ㅖᒸ ᫬ᕼ㸦኱Ꮫ㝔ᕤᏛ◊✲⛉⏕࿨⎔ቃ໬Ꮫᑓᨷ㸧 ኱⫼ᡞ ㇏㸦ዉⰋዪᏊ኱Ꮫ◊✲㝔⏕ά⎔ቃ⛉Ꮫ⣔㸧

Synthesis of Liquid Crystalline Nanosheet/Polyurethane Composite Elastomer Films

MIYAMOTO, Nobuyoshi

㸦

Department of Life, Environment, and Applied Chemistry, Faculty of Engineering

㸧

MOROOKA, Toki

㸦

Graduate School of Engineering, Department of Life, Environment, and Applied Chemistry

㸧

OHSEDO, Yutaka

㸦

Faculty of Human Life and Environment, Department of Computer Science and Clothing Environment, Nara

Women's University

㸧

Abstract

Inorganic nanosheet/polyurethane nanocomposite elastomers were synthesized in the form of thin films. To synthesize the composite film, layered clay mineral fluorohectorite was first exfoliated into single-layer nanosheets in N,N- dimethylformamide/water mixture added with the prepolymer, isocyanate-terminated low-molecular-weight poly(ethylene oxide).

The mixture was then contacted with the solution of four-functional crosslinker molecule, triethylenetetramine, resulting in the formation of urethane bonds that crosslink the prepolymers. The obtained composite elastomer films showed largely improved mechanical property compared to the elastomer without the nanosheets. The composite elastomer film will be applicable in many fields such as dielectric elastomer generator.

Keywords㸸nanosheet, polyurethane, nano-composite film

⥴ゝ

↓ᶵᒙ≧⤖ᬗࢆ๤㞳࣭ศᩓࡋ࡚ᚓࡽࢀࡿ↓ᶵࢼࣀࢩ࣮ࢺ ࡣཌࡉ

1nm

ࠊ⦪ᶓᖜᩘ༑

nm

ࠥᩘ

ȝm

࡜࠸࠺ᴟࡵ࡚኱ࡁ࡞ẚ

⾲㠃✚࡜࢔ࢫ࣌ࢡࢺẚࢆ᭷ࡍᚤ⢏Ꮚ࡛࠶ࡿࠋ↓ᶵࢼࣀࢩ࣮

ࢺࡣ㧗ศᏊ࡜ࢼࣀࢥ࣏ࣥࢪࢵࢺ໬¹ࡍࡿࡇ࡜࡛ప⃰ᗘ࡛ࡶ

኱ࡁ࡞ᙉᗘ²ࡸ⇕≀ᛶ³ࡢྥୖࡀᮇᚅ࡛ࡁࡿࡓࡵࠊࡇࢀࡲ

࡛࡟ከࡃࡢ◊✲ࡀ࡞ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊᚑ᮶ሗ࿌ࡉࢀ࡚

࠸ࡿࢼࣀࢥ࣏ࣥࢪࢵࢺ࡛ࡣࠊࢼࣀࢩ࣮ࢺࡢ㓄ྥࡸ✵㛫ศᕸ ࡀ༑ศ࡟ไᚚࡉࢀ࡚࠸࡞࠸ࡶࡢࡀ࡯࡜ࢇ࡝࡛࠶ࡾࠊࡲࡓ↓

ᶵࢼࣀࢩ࣮ࢺࡀ᏶඲࡟༢ᒙ࡟๤㞳ࡋ࡚࠸࡞࠸ࡶࡢࡶከ࠸ࠋ

୍᪉ࢼࣀࢩ࣮ࢺࡣࠊࡑࡢᴟࡵ࡚኱ࡁ࡞࢔ࢫ࣌ࢡࢺẚࢆ᭷

ࡍࡿᙧ≧ࡢࡓࡵࠊ⁐፹࡟ศᩓࡋࡓ≧ែ࡛⮬Ⓨⓗ࡟㓄ྥࡋᾮ ᬗ┦ࢆᙧᡂࡍࡿ^4-6ࠋࡑࡇ࡛ᡃࠎࡣࠊࡇࢀࡲ࡛࡟ࠊᾮᬗ≧ែ

ࡢ↓ᶵࢼࣀࢩ࣮ࢺ

/

Ỉࢥࣟ࢖ࢻ࡜ぶỈᛶࣔࣀ࣐࣮ࢆᆒ୍࡟ΰ

ྜࡋ࡚࠿ࡽ㔜ྜࡍࡿ

in-situ

ྜᡂἲ࡟ࡼࡗ࡚ࠊ↓ᶵࢼࣀࢩ࣮

ࢺ

/

ぶỈᛶ㧗ศᏊࢼࣀࢥ࣏ࣥࢪࢵࢺࢤࣝࢆሗ࿌ࡋ࡚ࡁࡓ^7-

9 ࠋࡇࢀࡽࡢࢤ࡛ࣝࡣࢼࣀࢩ࣮ࢺࡀ༢ᒙ࡛㧗ᗘ࡟ศᩓࡋ࡚

࠾ࡾࠊᾮᬗᵓ㐀ࢆಖᣢࡋࠊእሙ࡟ࡼࡿࢼࣀࢩ࣮ࢺࡢ㓄ྥไ ᚚࡶ࡞ࡉࢀ࡚࠸ࡿࠋࡇࢀࡽࡢࡇ࡜࡟ࡼࡗ࡚ࠊᙉᗘࡢ኱ᖜ࡞

ྥୖࡢࡳ࡞ࡽࡎࠊࡉࡲࡊࡲ࡞⯆࿡῝࠸␗᪉ⓗ࡞≉ᛶࡀぢࡽ

ࢀࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊ୍⯡࡟↓ᶵࢼࣀࢩ࣮ࢺࡣぶỈᛶ࡛࠶

ࡾ᭷ᶵ⁐፹࡬ࡢศᩓࡀᅔ㞴࡛࠶ࡿࡓࡵࠊᕤᴗⓗ࡟㔜せ࡞␯

Ỉᛶ㧗ศᏊ࠿ࡽ࡞ࡿ࢚ࣛࢫࢺ࣐࣮ᮦᩱ࡟ࡇࡢᡭἲࢆᛂ⏝ᒎ 㛤ࡍࡿࡢࡣ㞴ࡋ࠿ࡗࡓࠋ

ࡑࡢࡼ࠺࡞୰࡛ᡃࠎࡣ୍㒊ࡢࢼࣀࢩ࣮ࢺࡀỈ࡜᭷ᶵ⁐፹ ࡢΰྜ⁐፹୰࡛༢ᒙ๤㞳ࡋᾮᬗ┦ࢆᙧᡂࡍࡿࡇ࡜ࢆぢฟࡋ ࡓࠋࡇࡢࡇ࡜ࢆ฼⏝ࡋࠊỈ

/

᭷ᶵ⁐፹ΰྜ⁐፹ࢆ⏝࠸࡚ᾮᬗ

≧ែࡢ↓ᶵࢼࣀࢩ࣮ࢺ࡜࢖ࢯࢩ࢔ࢿ࣮ࢺᇶࢆᮎ➃࡟ᑟධࡋ ࡓࣉ࣏࣐࣮ࣞࣜࢆΰྜࡋࠊ

4

ᐁ⬟ࡢᯫᶫ๣࡛࠶ࡿࢺ࢚ࣜࢳ

ࣞࣥࢸࢺ࣑ࣛࣥ7(7$ࡢ⁐ᾮ୰࡟ᢲࡋฟࡍ࡜࠸࠺᪂ࡋ࠸᪉ ἲ࡟ࡼࡾࠊࣇ࢓࢖ࣂ࣮ᙧ≧ࡢ」ྜ࢚ࣛࢫࢺ࣐࣮ࢆྜᡂࡍࡿ

ࡇ࡜࡟᭱㏆ᡂຌࡋࡓ¹⁰ࠋࡇࡢࣇ࢓࢖ࣂ࣮ෆ࡛ࡣࠊࢼࣀࢩ࣮

ࢺࡢᾮᬗ≧ែ࡟㉳ᅉࡍࡿ࣓ࢰࢫࢣ࣮ࣝࡢᵓ㐀࡜ࠊᢲࡋฟࡋ

᫬࡟ᙧᡂࡉࢀࡿᕧどⓗ࡞㓄ྥࡀಖᣢࡉࢀ࡚࠾ࡾࠊຊᏛᙉᗘ

ࡶ኱ࡁࡃྥୖࡍࡿࡇ࡜ࡀぢฟࡉࢀࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊ✀ࠎ ࡢᛂ⏝࡟࠶ࡓࡗ࡚ࡣࠊࣇ࢓࢖ࣂ࣮௨እࡢᙧែ࡟ᡂᙧࡉࢀࡓ

࢚ࣛࢫࢺ࣐࣮ࡀᚲせ࡜࡞ࡗ࡚ࡃࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊୖ

グࡢྜᡂᡭἲ࡟ᇶ࡙࠸࡚ࠊⷧ⭷ᙧែࡢ」ྜ࢚ࣛࢫࢺ࣐࣮ࡢ

ྜᡂࢆヨࡳࡓࠋ ᐇ㦂᪉ἲ

ࢼࣀࢩ࣮ࢺࢥࣟ࢖ࢻࡢㄪ〇

ᅗ 䛚福岡工業大学総合研究機構研究所報　第4号（2021年10月）

(3)

ᐑඖ ᒎ⩏㸪ㅖᒸ ᫬ᕼ㸪኱⫼ᡞ ㇏

ࢺࣆ࣮ᕤᴗ♫〇ࡢࣇࣝ࢜ࣟ࡬ࢡࢺࣛ࢖ࢺ㸦)+7ࠊၟရྡ

1+7% ࢰࣝ㸧ࢆࠊ᪤ሗ࡟ᚑࡗ࡚㐲ᚰศ㞳࡟ࡼࡗ࡚⢭〇ࡋ

࡚ࠊ▼ⱥ࡞࡝ࡢ୙⣧≀ࢆ㝖ཤࡋࠊ⃰ᗘㄪᩚࢆ⾜࠸ࠊZWࡢ ࢼࣀࢩ࣮ࢺศᩓᾮࢆᚓࡓࠋࡉࡽ࡟ࠊ࢖࢜ࣥ஺᥮ᶞ⬡ࢆ⏝࠸

࡚ࠊࢼࣀࢩ࣮ࢺࡢᑐ࢝ࢳ࢜ࣥࢆ 1D࠿ࡽ 1+࡟஺᥮ࡋࡓࠋࡇ ࡢ 1+ᆺࢼࣀࢩ࣮ࢺỈศᩓ⁐ᾮࢆ⃰⦰ࡋࡓᚋࠊ

1 1

ࢪ࣓

ࢳ࣒ࣝ࣍ࣝ࢔࣑ࢻ'0)ࢆຍ࠼࡚⃰ᗘㄪᩚࡋࠊࢼࣀࢩ࣮ࢺ Ỉ'0) ࢥࣟ࢖ࢻࢆᚓࡓࠋ

ࣉ࣏࣐࣮ࣞࣜ⁐ᾮ࡜ᯫᶫ๣⁐ᾮࡢㄪ〇

ࣉ࣏࣐࣮ࣞࣜ⁐ᾮ࡜ᯫᶫ๣⁐ᾮࡣࠊ᪤ሗ ࡟ᇶ࡙ࡁ௨ୗ

ࡢᡭ㡰࡛ᚓࡓࠋ❅⣲㞺ᅖẼୗ࡛ P/ ࡢ㉸⬺Ỉ '0) ࡟ J PPROࡢ࣏࢚ࣜࢳࣞࣥࢢࣜࢥ࣮ࣝ3(*0Z ࢆຍ

࠼ࠊ࣐ࣥࢺࣝࣄ࣮ࢱ࣮࡛ Υ࡟ຍ⇕ࡋ࡚ 3(* ࢆ⁐ゎࡉࡏ ࡓࠋࡑࡢᚋࠊࣅࢫ࢖ࢯࢩ࢔ࢼࢺ࣓ࢳࣝࢩࢡࣟ࣊࢟ࢧࣥ

ࢆ J PPROຍ࠼ࠊࡉࡽ࡟ゐ፹࡜ࡋ࡚ J PPROࡢࢪࣛ࢘ࣜࣥ㓟ࢪࣈࢳࣝࢫࢬࢆῧຍࡋ Υ

࡛⣙ ᫬㛫ᨩᢾࡍࡿࡇ࡜࡛ࠊ3(* ࡢ୧ᮎ➃࡟࢖ࢯࢩ࢔ࢿ࣮ࢺ ᇶࡀᑟධࡉࢀࡓࣉ࣏࣐࣮ࣞࣜࡢ⁐ᾮࢆᚓࡓࠋࡉࡽ࡟ࣉ࣏ࣞ

࣐࣮ࣜ⁐ᾮ J ࡟ࢼࣀࢩ࣮ࢺỈ'0) ࢥࣟ࢖ࢻ RUJࢆຍ࠼࡚ࡼࡃᨩᢾࡋࠊ཯ᛂ๓㥑⁐ᾮ࡜ࡋ ࡓࠋࡲࡓᯫᶫ๣7(7$J ࡜ '0)J ࢆΰྜࡋࡓࡶࡢࢆᯫ

ᶫ๣⁐ᾮ࡜ࡋࡓࠋ

࢚ࣛࢫࢺ࣐࣮⭷ࡢྜᡂ

ࢩ࣮ࣕࣞࡢ୰࡟ࢩࣜࢥࣥࢦ࣒〇ࡢᆺࢆධࢀࠊࡑࡢᆺࡢ୰

࡟ࣉ࣏࣐࣮ࣞࣜ⁐ᾮࡲࡓࡣࢼࣀࢩ࣮ࢺࣉ࣏࣐࣮ࣞࣜΰྜ

⁐ᾮࢆ 㹥ධࢀࡓࠋࡑࡢᚋࠊ┿✵࣮࢜ࣈࣥ࡟ධࢀ࡚ࠊΥ

࡛ ศࠊࡉࡽ࡟ Υ࡛㸯᫬㛫஝⇱ࡉࡏࠊࣉ࣏࣐࣮ࣞࣜ⭷ࢆ

సᡂࡋࡓࠋࡑࡢᚋࠊࡇࡢ஝⇱ࡋࡓࣉ࣏࣐࣮ࣞࣜ⭷࡟ᯫᶫ๣

㸦7(7$ࡢ '0) ⁐ᾮࢆຍ࠼୍࡚᪥ᨺ⨨ࡋࡓࡢࡕࠊ┿✵࣮࢜ࣈ

࡛ࣥ Υ࣭ ᫬㛫஝⇱ࡉࡏ )+7࣏ࣜ࢘ࣞࢱࣥ」ྜ࢚ࣛࢫࢺ

࣐࣮⭷ࢆసᡂࡋࡓࠋ

࢚ࣛࢫࢺ࣐࣮⭷ࡢྜᡂ

◪Ꮚᯈࡢୖ࡟ࢩࣜࢥࣥࢦ࣒ࡢᆺࢆࡢࡏࠊᆺࡢ୰ࢆࣉ࣏ࣞ

࣐࣮ࣜ⁐ᾮ࡛඘ࡓࡋࡓᚋ࡟ࠊᆺࡈ࡜ᯫᶫ๣⁐ᾮ࡟ᾐₕࡍࡿ

ࡇ࡜࡛ࠊ࢚ࣛࢫࢺ࣐࣮⭷ࡢྜᡂࢆヨࡳࡓࠋࡲࡎࠊࢼࣀࢩ࣮

ࢺࣉ࣏࣐࣮ࣞࣜ⁐ᾮ 㹥ࢆ࢞ࣛࢫᯈࡢୖ࡟ࡢࡏࡓࢩࣜࢥ

ࣥࢦ࣒ࡢᆺ࡟ὶࡋ㎸ࢇࡔࠋࡑࡢᚋࠊΥ࡟ຍ⇕ࡋࡓࠊᯫ

ᶫ๣7(7$ࡢ '0) ⁐ᾮ㸦ZW㸧࡟ ศᾐࡋࡓࠋࡑࡢᚋࠊ '0) ࡛⭾₶ࡋࡓ )+7࣏ࣜ࢘ࣞࢱ࢚ࣥࣛࢫࢺ࣐࣮ࢆ┿✵࣮࢜

ࣈ࡛ࣥ Υ࣭㸯᫬㛫஝⇱ࡉࡏࡿࡇ࡜࡛ࠊࢼࣀࢩ࣮ࢺ࣏ࣜ

࢘ࣞࢱࣥ」ྜ࢚ࣛࢫࢺ࣐࣮⭷ࢆసᡂࡋࡓࠋ

࢟ࣕࣛࢡࢱࣜࢮ࣮ࢩࣙࣥ

ࢼࣀࢩ࣮ࢺ

/

Ỉ

/DMF

ࢥࣟ࢖ࢻ࠾ࡼࡧࣉ࣏࣐࣮ࣞࣜ⁐ᾮࢆ

஝⇱ࡉࡏࡓࢧࣥࣉࣝ࠾ࡼࡧࣇ࢓࢖ࣂ࣮ࢆࣇ࣮࢚ࣜኚ᥮㉥እ ศගගᗘィ

(FT-IR, Agilent Technologies, Cary670)

࡛ ᐃࡋ ࡓࠋᘬᙇヨ㦂ࡣ

Shimadzu

♫ࡢ

EZ-L

ࢆ⏝࠸࡚⾜ࡗࡓࠋ

㻟㻚㻌⤖ᯝཬࡧ⪃ᐹ㻌

ࡲࡎ஝⇱ࣉ࣏࣐࣮ࣞࣜ⭷ࢆస〇ࡋ࡚࠿ࡽࠊᯫᶫ๣࡟ᾐₕ ࡋ࡚ᯫᶫࢆ⾜࠺᪉ἲ࡛ࡢ࢚ࣛࢫࢺ࣐࣮⭷ࡢస〇ࢆヨࡳࡓࠋ ࢼࣀࢩ࣮ࢺࢆຍ࠼ࡎ࡟స〇ࡋࡓ⭷ࡣᆒ୍࡛㏱࡛᫂ᙎຊࡀ࠶

ࡾࠊ㸱ಸ⛬ᗘࡲ࡛ᘬࡗᙇࡿࡇ࡜ࡢฟ᮶ࡿᙉᗘࢆ᭷ࡋ࡚࠸ࡓ 㸦ᅗ㸯ᕥ㸧ࠋ୍᪉ࠊࢼࣀࢩ࣮ࢺࢆ

1.5

㹵㹲㸣ྵ᭷ࡍࡿࣉࣞ

࣏࣐࣮ࣜ⭷ࢆᯫᶫࡋࡓሙྜࠊࢧࣥࣉࣝෆ㒊࡟ẼἻࡀከᩘ⏕

ࡌࡓ㸦ᅗ㸯ྑ㸧ࠋࡇࢀࡣࠊࢼࣀࢩ࣮ࢺ⁐ᾮ࡜ࣉ࣏࣐࣮ࣞࣜ

⁐ᾮࢆΰྜࡋࡓ㝿࡟ࠊࢼࣀࢩ࣮ࢺ⁐ᾮ࡟ྵࡲࢀࡿỈ࡜ࣉࣞ

࣏࣐࣮ࣜᮎ➃ࡢ࢖ࢯࢩ࢔ࢿ࣮ࢺᇶࡀ཯ᛂࡋࠊ஧㓟໬Ⅳ⣲ࡀ

⏕ᡂࡋࡓࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡓࠋ

2

ᾮࢆΰྜࡋ࡚࠿ࡽ஝

⇱ࣉࣟࢭࢫ࡟㐍ࡴࡲ࡛ࡢ᫬㛫ࢆ▷ࡃࡋࡓሙྜࠊⓎἻࡀᢚไ ࡉࢀࡿࡇ࡜ࡶࢃ࠿ࡗ࡚ࡁࡓࡢ࡛ࠊ௒ᚋࠊྜᡂࣉࣟࢭࢫࡢࡉ

ࡽ࡞ࡿ᭱㐺໬ࢆ⾜࠺ࡇ࡜࡛ࡼࡾࠊᆒ୍࡞ࢧࣥࣉࣝࡀᚓࡽࢀ

ࡿࡢ࡛ࡣ࡞࠸࠿࡜⪃࠼ࡽࢀࡿࠋ

ḟ࡟ࠊᆺᯟ࡟ࣉ࣏࣐࣮ࣞࣜ⁐ᾮࢆ඘ࡓࡋࠊࡑࡢᆺᯟࡈ࡜

ᯫᶫ๣⁐ᾮ࡟ᾐₕࡍࡿ᪉ἲ࡛ࡢ࢚ࣛࢫࢺ࣐࣮⭷ࡢస〇ࢆヨ

ࡳࡓࠋࡇࡢ᪉ἲ࡛ᚓࡽࢀࡓࢼࣀࢩ࣮ࢺ

/

࣏ࣜ࢘ࣞࢱࣥ」ྜ࢚

ࣛࢫࢺ࣐࣮⭷ࡢࢧࣥࣉࣝࡢ෗┿ࢆᅗ㸰࡟♧ࡍࠋࡇࡢ᪉ἲ࡛

ࡣࠊࣉ࣏࣐࣮ࣞࣜ⁐ᾮࡀᯫᶫࡉࢀࡿ๓࡟ᣑᩓࡋ࡚ࡋࡲ࠺ࡇ ᅗ

2

㻚㻌䝥䝺䝫䝸䝬䞊⁐ᾮ䜢ᆺᯟ䛤䛸ᯫᶫ๣⁐ᾮ䛻ᾐₕ䛧䛶 ᚓ䜙䜜䛯䝘䝜䝅䞊䝖㻛䝫䝸䜴䝺䝍䞁」ྜ䜶䝷䝇䝖䝬䞊⭷䛾෗

┿䚹㻌㻔㼍㻕䛿స〇┤ᚋ䛾⭾₶ヨᩱ䚸㻔㼎㻕䛿஝⇱䛧䛯䜶䝷䝇䝖䝬䞊ヨᩱ䚹

㻌㻌

ᅗ

1

㻚㻌 ஝⇱䝥䝺䝫䝸䝬䞊⭷䛛䜙స〇䛧䛯㻔ᕥ㻕䝫䝸䜴䝺䝍䞁⭷

䛚䜘䜃䠄ྑ䠅䝘䝜䝅䞊䝖㻛䝫䝸䜴䝺䝍䞁」ྜ⭷䛾෗┿䚹

(4)

ᾮᬗᛶ↓ᶵࢼࣀࢩ࣮ࢺ

/

࣏ࣜ࢘ࣞࢱࣥ」ྜ࢚ࣛࢫࢺ࣐࣮⭷ࡢྜᡂ

࡜࡞࡝ࡀᠱᛕࡉࢀࡓࡀࠊࡑࡢࡼ࠺࡞⌧㇟ࡣ㉳ࡇࡽࡎࠊἻࡢ

Ⓨ⏕ࡶᢚไࡉࢀࠊẚ㍑ⓗᆒ୍࡞ࢧࣥࣉࣝࡀᚓࡽࢀࡓࠋ ࡉࡽ࡟ྜᡂࡢ☜ㄆࢆ⾜࠺ࡓࡵࠊ࣏ࣜ࢘ࣞࢱ࢚ࣥࣛࢫࢺ࣐

࣮ࠊࢼࣀࢩ࣮ࢺࠊࢼࣀࢩ࣮ࢺ

/

࣏ࣜ࢘ࣞࢱࣥ」ྜ࢚ࣛࢫࢺ࣐

࣮ࡢ

FT-IR

ࢫ࣌ࢡࢺࣝ ᐃࢆ⾜ࡗࡓ㸦ᅗ

3

㸧ࠋ࣏ࣜ࢘ࣞࢱ

࢚ࣥࣛࢫࢺ࣐࣮ࡲࡓࡣࢼࣀࢩ࣮ࢺ

/

࣏ࣜ࢘ࣞࢱ࢚ࣥࣛࢫࢺ࣐

࣮࡛ࡣࠊ࢘ࣞࢱࣥ⤖ྜ

(-NH-COO-)

ࡢᏑᅾࢆ♧ࡍ

1713 cm

^-1 㸦

C=O

ఙ⦰᣺ື㸧ࡢᙅ࠸ࣆ࣮ࢡ࡜

1553 cm

^-1

(amide II)

ࡢ ᙉ࠸ࣆ࣮ࢡࡀ࠶ࡽࢃࢀ࡚࠸ࡿࠋࡲࡓࠊ㧗ศᏊࡢෆ࡟ከࡃᏑ ᅾࡍࡿ

C-H

⤖ྜ࡟ࡼࡿࠊ

2918cm

^-1

, 2856cm

^-1

(C-H

ఙ⦰᣺

ື㸧࡜

1454 cm

^-1

(C-H

ኚゅ᣺ື㸧ࡢࣆ࣮ࢡࡶぢࡽࢀࡿࠋ

1651 cm

^-1ࡢࣆ࣮ࢡࡣࢼࣀࢩ࣮ࢺࡢࡳࡢሙྜ࡛ࡶぢࡽࢀ࡚

࠾ࡾࠊࡇࢀࡣࢼࣀࢩ࣮ࢺࡢᑐ࢝ࢳ࡛࢜ࣥ࠶ࡿ࢔ࣥࣔࢽ࣒࢘

࢖࢜ࣥ࡟㉳ᅉࡍࡿ

N-H

ኚゅ᣺ື࡟ᖐᒓࡉࢀࡿࠋ

ࡇࡢࡼ࠺࡟ࡋ࡚ᚓࡽࢀࡓࠊࢼࣀࢩ࣮ࢺ

/

࣏ࣜ࢘ࣞࢱࣥ」ྜ

࢚ࣛࢫࢺ࣐࣮

(

ࢼࣀࢩ࣮ࢺ

10wt%

ྵ᭷㸧ࡣඃࢀࡓຊᏛᙉᗘ

ࢆ♧ࡋࡓࠋᅗ

4

࡟ᘬᙇࡾヨ㦂ࡢ⤖ᯝࢆࠊᅗ

5

࡟ࡣ◚᩿Ⅼ௜

㏆࡛ࡢࢧࣥࣉࣝࡢ෗┿ࢆ♧ࡋࡓࠋࡇࡢ⤖ᯝࡼࡾࠊࢼࣀࢩ࣮

ࢺࢆ」ྜ໬ࡋ࡚࠸࡞࠸࣏ࣜ࢘ࣞࢱࣥ⭷࡟ẚ࡭ࠊ◚᩿ఙࡧࠊ

◚᩿ᛂຊ࡜ࡶ኱ࡁࡃྥୖࡋࡓࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡇࢀ

ࡣࠊᆒ୍࡟ᑟධࡉࢀࡓࢼࣀࢩ࣮ࢺ࡟ࡼࡿ⿵ᙉຠᯝࡀ኱ࡁࡃ స⏝ࡋࡓࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ

㻠㻚㻌 ⤖ㄽ㻌

ⷧ⭷≧࡟ᡂᙧࡋࡓࢼࣀࢩ࣮ࢺᾮᬗ

/

࣏ࣜ࢘ࣞࢱࣥ」ྜ࢚ࣛࢫ ࢺ࣐࣮ࡢస〇࡟ᡂຌࡋࡓࠋ」ྜ࢚ࣛࢫࢺ࣐࣮ࡣࢼࣀࢩ࣮ࢺ

୙ΰྜࡋ࡚࠸࡞࠸࢚ࣛࢫࢺ࣐࣮࡜ẚ㍑ࡋ࡚㧗࠸ຊᏛ≉ᛶࢆ

♧ࡋࡓࠋ௒ᚋࠊࡉࡽ࡟ྜᡂ᮲௳ࡸྜᡂࣉࣟࢭࢫࢆ᭱㐺໬ࡍ

ࡿࡇ࡜࡟ࡼࡗ࡚ࠊᵓ㐀ᮦᩱࡸࠊㄏ㟁࢚ࣛࢫࢺ࣐࣮ᆺⓎ㟁ࢹ

ࣂ࢖ࢫ➼࡟ᖜᗈࡃᛂ⏝ࡉࢀࡿࡇ࡜ࡀᮇᚅࡉࢀࡿࠋ

㻡㻚㻌ㅰ㎡㻌

ᮏ◊✲ࡢ୍㒊ࡣࠊ⚟ᒸᕤᴗ኱Ꮫ

2019

ᖺᗘ◊✲㧗ᗘ໬ᨭ᥼

ไᗘ࠾ࡼࡧࠊ≀㉁࢚ࢿࣝࢠ࣮ࢹࣂ࢖ࢫ◊✲ࢭࣥࢱ࣮

(

ᩥ㒊⛉

Ꮫ┬⚾❧኱Ꮫᡓ␎ⓗ◊✲ᇶ┙ᙧᡂᨭ᥼஦ᴗ

#S1511036L)

ࡢᨭ᥼ࢆཷࡅ࡚ᐇ᪋ࡉࢀࡲࡋࡓࠋࡇࡇ࡟グࡋ࡚ࠊᚚ♩⏦ࡋ

ୖࡆࡲࡍࠋ

ᩥ ⊩

Usuki, A.; Kojima, Y.; Kawasumi, M.; Okada, A.; Fukushima, Y.; Kurauchi, T.;

Kamigaito, O., Synthesis of of nylon 6-clay hybrid. J. Mater. Res.8, 1179-1184 (1993).

Liff, S. M.; Kumar, N.; McKinley, G. H., High-performance elastomeric nanocomposites via solvent-exchange processing. Nat. Mater.6 (1), 76-83 (2007).

Gilman, J. W.; Jackson, C. L.; Morgan, A. B.; Jr., R. H.; Wuthenow, E. M. E. P.

G. M.; Hilton, D.; Phillips, S. H., Flammability Properties of PolymerʷLayered- Silicate Nanocomposites. Polypropylene and Polystyrene Nanocomposites. Chem.

Mater.12, 1866-1873 (2000).

Miyamoto, N.; Iijima, H.; Ohkubo, H.; Yamauchi, Y., Liquid crystal phases in the aqueous colloids of size-controlled fluorinated layered clay mineral nanosheets. Chem.

Commun.46, 4166-4168 (2010).

Miyamoto, N.; Yamamoto, H.; Kaito, R.; Kuroda, K., Formation of extraordinarily large nanosheets from K4Nb6O17 crystals. Chem. Commun., 2378- 2379 (2002).

Miyamoto, N.; Nakato, T., Liquid crystalline nature of K4Nb6O17 nanosheet sols and their macroscopic alignment. Adv. Mater.14 (18), 1267-1270 (2002).

Shintate, M.; Inadomi, T.; Yamamoto, S.; Kuboyama, Y.; Ohsedo, Y.; Arimura, T.; Nakazumi, T.; Hara, Y.; Miyamoto, N., Anisotropic self-oscillating reaction in liquid crystalline nanosheets hydrogels. J. Phys. Chem. B122, 2957–2961 (2018).

Inadomi, T.; Ikeda, S.; Okumura, Y.; Kikuchi, H.; Miyamoto, N., Photo-Induced Anomalous Deformation of Poly(N-Isopropylacrylamide) Gel Hybridized with an Inorganic Nanosheet Liquid Crystal Aligned by Electric Field. Macromol. Rapid Commun.35, 1741-1746 (2014).

㻌

ᅗ 㻠㻚㻌㻔㼍㻕䝫䝸䜴䝺䝍䞁⭷䛚䜘䜃㻔㼎㻕䝘䝜䝅䞊䝖㻛䝫䝸䜴䝺䝍䞁」

ྜ⭷䛾ᘬᙇ䜚ヨ㦂⤖ᯝ䚹

ᅗ

3

㻚㻌㻔㼍㻕䝥䝺䝫䝸䝬䞊䚸㻔㼎㻕䝫䝸䜴䝺䝍䞁䜶䝷䝇䝖䝬䞊䚸㻔㼏㻕䝘䝜䝅䞊䝖䚸㻔㼐㻕䝘䝜䝅䞊䝖㻛䝫䝸䜴䝺䝍䞁」ྜ䜶䝷䝇䝖䝬䞊䛾㻲㼀㻵㻾䝇䝨䜽䝖䝹㻌

(5)

ᐑඖ ᒎ⩏㸪ㅖᒸ ᫬ᕼ㸪኱⫼ᡞ ㇏

Miyamoto, N.; Shintate, M.; Ikeda, M.; Hoshida, Y.; Yamauchi, Y.; Annaka, M., Liquid Crystalline Inorganic Nanosheets for Facile Synthesis of Polymer Hydrogels with Anisotropies in Optical Property, Structure, Swelling/Deswelling, and Ion Transport/Fixation. Chem. Commun.49, 1082-1084 (2013).

Morooka, T.; Ohsedo, Y.; Kato, R.; Miyamoto, N., Structure-regulated tough elastomer of liquid crystalline inorganic nanosheets/polyurethane nanocomposite.

Mater. Adv.2, 1035-1042 (2021).

⚟ᒸᕤᴗ኱Ꮫ◊✲ᡤᡤሗ㸦

2020

㸧

ࣇ࢙ࢽࣝ࣎ࣟࣥ㓟ㄏᑟయࢆྵࡴ⬡㉁㧗ศᏊ⭷ࢆ⏝࠸ࡓ 㟁఩ᆺ⢾㢮⏝⏑࿡ࢭࣥࢧ࡟㛵ࡍࡿ◊✲

ᕩ 㟅㸦㟁Ꮚ᝟ሗᕤᏛ⛉㸧

Research on a Potentiometric Sweetness Sensor for Sugars using a Lipid Polymer Membrane Containing a Phenylboronic Acid Derivative

WU Xiao

㸦

Department of Information Electronics

㸧

Abstract

The boronic acids are significant functional groups for design of chemical sensors for sugar recognition, because they are known to form ester with diols. In this study, we report a research on responses to uncharged sweet substances using a lipid polymer membrane consisting of tetradodecylammonium bromide (TDAB) as a lipid, dioctyl phenylphosphonate (DOPP) as a plasticizer and 3-nitrophenylboronic acid (3-NPBA) as a sugar recognition site. This sensor showed positive changes in membrane potentials to uncharged sugars such as monosaccharides and sugar alcohols, while no response to disaccharides such as sucrose or sucralose.

Moreover, the sensor response has a positive correlation with the concentration of boric acid (0-5%). The results revealed that the phenylboronic acid derivative could be a useful functional substance in a lipid polymer membrane of a potentiometric sweetness sensor for detecting electrically neutral sugars.

Keywords㸸

potentiometric sweetness sensor, lipid polymer membrane, phenylboronic acid derivative, diol group

ࡣࡌࡵ࡟

ேࡀឤࡌࡿ࿡ࡣࠊᗈ⩏ࡢព࿡࡜⊃⩏ࡢព࿡࡟ศࡅࡽࢀࡿࠋ ᗈ⩏ࡢព࿡࡛ࡣࠊ࿡ࡣ࿡ぬࡔࡅ࡛ࡣ࡞ࡃࠊႥぬࠊゐぬࠊどぬࠊ

⫈ぬࢆྜࢃࡏࡓ஬ឤࠊ᭦࡟ࡣᚰ㌟ࡢ≧ែࠊ㣗⩦័ࡸ㣗⎔ቃ࡞

࡝ࡢ᪥ᖖⓗ᮲௳ࡶ㛵୚ࡋ࡚࠸ࡿࠋ୍᪉ࠊ⊃⩏ࡢព࿡࡛ࡢ࿡

ࡣࠊ⯉ࡢ࿡⣽⬊࡛ឤࡌࡿ࿡㸦໬Ꮫⓗ࡞࿡㸧ࡢࡇ࡜ࢆゝ࠺ࠋ࿡

⣽⬊࡛ཷᐜࡉࢀࡿ࿡ࡣࠊᇶᮏ஬࿡࡜࿧ࡤࢀࡿሷ࿡ࠊ㓟࿡ࠊ࠺

ࡲ࿡ࠊⱞ࿡ࠊ⏑࿡࠿ࡽᵓᡂࡉࢀ࡚࠸ࡿ¹ࠋᇶᮏ஬࿡ࡣࠊᡃࠎ ࡢయ࡟࡜ࡗ࡚㔜せ࡞ព࿡ࡸ≉ᚩࢆᣢࡗ࡚࠸ࡿࠋ౛࠼ࡤࠊሷ࿡

ࡣ㟁ゎ㉁ࡢ᭷↓ࢆ♧ࡋࠊ⏕యෆࡢ㟁ゎ㉁ࡢࣂࣛࣥࢫࢆㄪᩚ

ࡍࡿࡢ࡟ᚲせ࡞࣑ࢿࣛࣝ※࡜࡞ࡿࠋ㓟࿡ࡣࠊ⭉ᩋࡢࢩࢢࢼࣝ

࡛࠶ࡾࠊ㓑㓟ࡸࢡ࢚ࣥ㓟࡞࡝ࡀᣲࡆࡽࢀࡿࠋ࠺ࡲ࿡ࡣ⏕≀࡟

୙ྍḞ࡞࢔࣑ࣀ㓟ࡢᏑᅾࢆ♧ࡋࠊࢢࣝࢱ࣑ࣥ㓟ࢼࢺ࣒ࣜ࢘

ࡸ࢖ࣀࢩࣥ㓟ࢼࢺ࣒ࣜ࢘࡞࡝ࡀ࠶ࡿࠋⱞ࿡ࡣẘᛶࡢ㆙࿌ࢆ

⾲ࡍࡶࡢ࡛ࠊ࢝ࣇ࢙࢖ࣥࡸ࢟ࢼࡢᶞ⓶࡟ྵࡲࢀࡿ࢟ࢽ࣮ࢿ

࡞࡝ࡀ࠶ࡿࠋ⏑࿡ࡣ⏕యෆ࡛࢚ࢿࣝࢠ࣮※࡜࡞ࡿ⢾ࡢᏑᅾ

ࢆ♧ࡋ࡚࠾ࡾࠊᩘከࡃࡢ✀㢮ࡀᏑᅾࡍࡿࠋ୺せ࡞ศ㢮ࡔࡅ࡛

ࡶࠊ⢾㢮㸦ࢫࢡ࣮ࣟࢫࠊࢢࣝࢥ࣮ࢫ➼㸧ࡸ⢾࢔ࣝࢥ࣮ࣝ㸦࢟

ࢩࣜࢺ࣮ࣝ➼㸧ࠊࢫࣝ࣍ࢽࣝ࢔࣑ࢻ㸦ࢧࢵ࢝ࣜࣥࢼࢺ࣒ࣜ࢘㸧

➼ࠊ࣌ࣉࢳࢻ㢮㸦࢔ࢫࣃࣝࢸ࣮࣒➼㸧ࡸ

D-

࢔࣑ࣀ㓟㸦

D-

ࢺ

ࣜࣉࢺࣇ࢓ࣥ➼㸧ࠊ⏑࿡ࢱࣥࣃࢡ㉁㸦ࢱ࣐࢘ࢳࣥ➼㸧࡜ࠊ໬

Ꮫᵓ㐀ࡶศᏊࢧ࢖ࢬࡶᵝࠎ࡞ࡶࡢࡀᏑᅾࡍࡿࠋ⏑࿡ཷᐜయ

ࡣ

G

⺮ⓑඹᙺᆺཷᐜయ࡛࠶ࡿ

T1R2

ཬࡧ

T1R3

ࡀ⤌ࡳྜࢃ ࡉࡗࡓ࣊ࢸࣟ」ྜཷᐜయ࡛࠶ࡿࠋࡇࡢ༢୍ࡢ⏑࿡ཷᐜయୖ

࡟」ᩘࡢ㒊఩㸦ࢧ࢖ࢺ㸧ࡀ࠶ࡿ࠿ࡽࡇࡑࠊ✀ࠎࡢ⏑࿡≀㉁ࢆ ᗈࡃཷᐜࡍࡿ஦ࡀฟ᮶ࡿࠋ⏑࿡ཷᐜయࡢゎ᫂࡜క࠸ࠊ⏑࿡≀

㉁࡟ඹ㏻ࡍࡿᵓ㐀ⓗ≉ᚩࡢ✲᫂ࡶ⾜ࢃࢀ࡚ࡁࡓ ^2,3ࠋ࡞࠿࡛

ࡶ

R. S. Shallenberger

ࡀᥦၐࡋࡓ

AH-B

ㄝࡀ⌧ᅾ᭱ࡶᗈࡃཷ ࡅධࢀࡽࢀ࡚࠸ࡿࡀࠊ⏑࿡≀㉁≉᭷ࡢඹ㏻Ⅼࢆㄝ᫂ࡍࡿ࡟ ࡣ⮳ࡗ࡚࠸࡞࠸⁴ࠋ

㣗ရ࣭㣧ᩱ࣓࣮࣮࢝࡟࠾ࡅࡿ㣗ရࡢ࿡ࡢホ౯ࡣࠊᐁ⬟ࣃࢿ

࣮ࣛࡀᐇ㝿࡟࿡ࢃ࠸ホ౯ࡍࡿᐁ⬟ヨ㦂ࡀ⾜ࢃࢀ࡚࠸ࡿࡀࠊ

ࣃࢿ࣮ࣛྛேࡢಶேᕪࡸయㄪ➼ࡢᙳ㡪࡟ࡼࡿࣂࣛࢶ࢟ࡀ⏕

ᅗ

1

࿡ㄆ㆑⿦⨨࡜ࢭࣥࢧ㟁ᴟ

Fig. 1. Taste sensing system and a working

electrode.

福岡工業大学総合研究機構研究所報　第4号（2021年10月）

福岡工業大学 学術機関リポジトリ